N-substituted iminocoumarin dyes

ABSTRACT

A 7-amino-2-iminocoumarin derivative bearing an aromatic or heteroaromatic radical in the 3-position. The compounds are valuable dyes which give bright mostly yellow colorations, particularly on polyesters.

0 United States Patent 1 3,910,912 Scheuermann et al. Oct. 7, 1975 [54]N-SUBSTITUTED IMINOCOUMARIN DYES 8189.773 1/1975 Boehmke H 260/307 R[75] Inventors: Horst Scheuermann; Qietmar FOREIGN PATENTS ORAPPLICATIONS Augart, both of Ludwigshafen; g g Mach, Hockenhfiim a of556,375 11/1974 Swltzerland 260/307 Germany OTHER PUBLICATIONS [73]Asslgnee: fifi z g rirg f s ?g:} Gore et al., Chemistry of Natural andSynthetic Co- German; g louring Matters, 1962, p.

. Venkataraman, The Chemistry of Synthetic Dyes, V01.

[22] II. pp- 775, 1034-1035, ibid Vol. IV, pp. 362-368,

[21] 362,900 lbid Vol. IV, pp. 362-368.

[30] Foreign Application Priority Data Primary Emml-ner DOna|d Daus May30, 1972 Germany 222621 1 A /nan: ExaminerDavid E, Wheeler Attorney,Agent, or Firm-Johnston, Keil, Thompson [52] U.S. Cl. 260/2564 Q;260/250 Q: & Shurtleff 260/2565 R; 260/304; 260/306.8 R; 260/3068 D;260/3092; 260/3322 A: 260/3452; 260/347.5; 260/242; 260/299; [57]ABSTRACT A 7-amm02-|m|nocoumarm derivative bearing an ari i i omatic 0rheteroaromatic radical in the 3position. 0 can: The compounds arevaluable dyes which give bright neurones Cited mostly yellowcolorations, particularly on polyesters.

UNITED STATES PATENTS 3 Claims, No Drawings 3,704,302 11/1972 Euomoto eta1, 260/2564 Q N-SUBSTITUTED IMINOCOUMARIN DYES The invention relates todyes of the formula (I):

in which A is hydrogen or alkyl of one to four carbon atoms;

B is an aromatic or heterocyclic radical;

R is hydroxy, substituted amino or an aliphatic, cy-

cloaliphatic, araliphatic, aromatic or hetcrocyclic radical;

R is hydrogen or unsubstituted or substituted alkyl,

cycloalkyl or aralkyl;

R is hydrogen or unsubstituted or substituted alkyl,

cycloalkyl or aralkyl;

R and R together with the nitrogen may be a heteroeyclie ring; and

n is l or 2.

Examples of alkyl radicals A are ethyl, propyl butyl and preferablymethyl.

Examples of radicals B are phenyl, phenyl bearing chloro, bromo, methyl,ethyl, ethoxy, methoxy, cyano, nitro, carboxyl, carbalkoxy, carbamoyl,N-substituted carbamoyl, sulphonic ester sulfonamido, N-substitutedsulfonamido or alkylsulfonyl as a substituent, naphthyl, thenyl orfuryl, benzimidazolyl, bcnzothiazolyl, benzoxazolyl,3,4-dihydro-4-oxoquinazolyl-(2) and 3,4- dihydro-3-oxoquinoxalyl-( 2Specific examples of B apart from those already given are:o-cyanophenyl, p-cyanophenyl, pnitrophcnyl, 2chloro-4-cyanophenyl,2-bromo-4- cyanophenyl, 2-chloro-4-nitrophenyl, 2,6-dichloro-4-nitrophenyl. 2-methyl-4-cyanophenyl, 2-methyl-4- nitrophenyl,2-ethoxy-4-cyanophenyl, 2-methoxy-4- nitrophenyl,2-carbomethoxy-4-cyanophenyl, 4-carboethoxyphenyl, 4-carbamoylphenyl,4-(N-methylcarbamoyl )-phenyl, 4-( N,N-diethylcarbamoyl )-phenyl,4-ethoxysulfonylphenyl, 4-butoxysulfonylphenyl, 4-dimethylaminosulfonylphcnyl, 4- dibutylaminosultonylphenyl,4-methylsulfonylphenyl, 4-ethylsultonylphenyl, 5carbomethoxyphcnyl,5-carboethoxyphenyl, S-carbobutoxyphenyl, 5- cyanothenyl,4-carhamoylthenyl, S-carbomethoxyfuryl. 5 -carboethoxyfuryl5-carbobutoxyfuryl, 5- cyanofuryl, S-carbamoylfuryl, N-methylbenzimidazolyl, N-benzylbcnzimidazolyl, N- phenylbcnzirnidazolyl,S-methylbenzimidazolyl, 5- chlorobenzimidazolyl,5-mcthoxybenzimidazolyl, 5-

chlorobenzothiazolyl, 5-chlorobenzoxazolyl, S-methylbenzoxazolyl,7-chloro-3,4-dihydro-4-oxoquinazolyl- (2) or3,4-dihydro-4-methyl-3-oxoquinoxalyl-(2).

The radical B may moreover be a quaternary group having one of theformulae:

in; I 1; 13

or the corresponding derivatives bearing chloro, methyl or methoxy as asubstituent in the benzene ring. Not only methyl and ethyl but alsohydroxyethyl, hydroxypropyl and B-hydroxy-y-chloropropyl are suitable asquaternizing radicals and they may be introduced by quaternization withthe appropriate epoxides.

Examples of radicals R are alkyl of one to eight carbon atoms, alkyl oftwo to eight carbon atoms bearing hydroxy, alkoxy, acyloxy, amino orN-substituted amino as a substituent, alkylene of two to six carbonatoms, unsubstituted or substituted phenyl and heterocyclic radicalswhich may bear chloro, methyl or methoxy as a substituent.

Specific examples of R are as follows: methyl, ethyl, propyl, butyl,hexyl, B-ethylhexyl, B-hydroxyethyl, B'hydroxypropyl, 'y-hydroxypropyl,B-methoxyethyl, B-ethoxyethyl, 'y-methoxypropyl, "y-ethoxypropyl,y-hexoxypropyl, 'y-acetoxypropyl, 'y-propionylpropyl,y-benzoyloxypropyl, 'y-dimethylaminopropyl, y-dibutylaminopropyl,'y-trimethylammoniumpropyl, 7-methyldibutylammoniumpropyl,y-ethyldibutylammoniumpropyl, 'y-ethyldimethylammoniumpropyl,B-aminoethyl,w-aminohexyl, dimethylene, tetramethylene, hexamethylene,cyclohexyl, benzyl, phenylethyl, phenyl, ehlorophenyl, dichlorophenyl,trichlorophenyl, methylphenyl, dimethylphenyl, ethylphenyl,methoxyphenyl, ethoxyphenyl, carboxylphenyl, carbamoylphenyl,sulfamoylphenyl, aminophenyl, dimethylaminophenyl, phenylaminophenyl,phcnylaminocarbonylaminophenyl, benzoylaminophcnyl,methoxycarbonylphenyl, ethoxycarbonylphenyl, butoxycarbonylphenyl,phenylene, diphenylenemethane and phenylamino; Z-benzothiazolyl,Z-imidazolyl, Z-(N-methyl benzothiazolium,2-(N,N'-dimethyl)-imidazolium, 2- pyridyl, 2-(4-methyl-5-acetyl)-thiazolyl, 2-( 4,5- diphenyl )-thiazolyl, 2-( 4,5-dimethyl)-thiazoly|, 2-( 4- methyl-5-carbomethoxy)-thiazolyl, 2-( 4-phenyl-5-earbomethoxy)-thiazolyl, 2-(4.5-di-p-methoxyphenyl thiazolyl, 2-(3,4-dimethyl-5-acetyl )-thiazolium, 2-( 3- methyl-4,5-diphenyl)-thiazolium, 2-( 3-ethyl-4,S- dimethyl )-thiazolium, 2-(3-ethyl-4,S-di-p-methoxyphenyl )thiazolium, 5-( 3-S-methyll,2,4-thiadiazolyl 5-( 3-B-carbomethoxyethylmercapto l 2,4- thiadiazolyl)and 5-( N-methyl-B-S-methyL l ,2.4- thiadiazolium Suitable anions forthe dyes containing quaternary groups are simple or complex inorganic ororganic anions. Specific examplcs are: chloride, bromide, sulfate,methosulfate, ethosulfate, nitrate. thiocyanate, tetraehlorozincate,tetrafluoborate. formate, acetate and toluencsulfonate.

Examples of radicals R and R are: methyl, ethyl, npropyl, isopropyl,n-butyl, isobutyl. B-mcthoxyethyl, B-ethoxyethyl, fi-acetoxyethyl.B-chlorocthyl. B-carbomethoxyethyl, B-carhoethoxyethyl,B-carbobutoxyethyl, B-methoxypropyl. B-cthoxypropyl.B-methoxyy-chloropropyl and B-acetoxypropyl.

Examples of radicals formed by R and R together with the nitrogen arepyrrolidinc, piperidine, morpholine, piperazinc and N-methylpiperazine.

The new dyes have high brightness and the shades lie in the range fromyellow to red. They are suitable for dyeing textile material ofpolyamides. cellulose esters. acrylonitrile polymers and polyesters andalso for the production of bright textile prints based on pigmentedplastics and for the production of daylight fluorescent pigments.

Dyes of the formula (l) may be prepared by reacting a compound of theformula (II):

B BL NH R2/ with a primary amine of the formula (Ill):

(Ill) and if desired quaternizing the reaction product for theproduction of the quaternary compound.

Reaction products having free OH or NH groups may be acylatcd ifdesired.

Compounds of the formula (II) and their production are disclosed forexample in DOS l,6l9,567, DOS l.569.777 and DOS 2.|29.565.

Compounds in which A is not hydrogen may be prepared analogously tocompounds of formula (ll) in which A is hydrogen.

Reaction of component (ll) with component (III) is conveniently carriedout by heating in the presence of a solvent, component (lll) serving assolvent if desired. Examples of other solvents are: alcohols such asetha nol, propanol or butanol; glyeols such as ethylene glycol ordiethylene glycol; glycol ethers such as ethylene glycol monomethyl.monoethyl or monobutyl ether; hydrocarbons such as toluene or xylene;chlorohydrocarbons such as perehloroethylene or chlorobcnzene; anddimethylformamide, N-methylpyrrolidonc and dimethylsulfoxide.

Preferred reaction temperatures are from about 50 to 200C particularlyfrom 80 20 150C.

Quaternization, if carried out, is by conventional methods; examples ofquarternizing agents are alkyl halides and particularly dialkylsulfates.

If an acylation is desired it is carried out by a conventional method,for example with an acid chloride or isocyanatcv Examples of primaryamines of the formula (III) are: methylamine, ethylamine, n-propylamine,isopropylamine, n-butylamine, isobutylamine and hexylamine;fiethylhexylamine. B-hydroxyethylamine, B-hydroxypropylamine,'y-hydroxypropylamine, B-methoxyethylamine, B-ethoxyethylamine,y-methoxypropylamine, y-ethoxypropylamine; 'y-hexoxypropylarnine,'y-acetoxypropylamine, y-propionyloxypropylamine,'y-benzoyloxypropylamine, 'y-dimethylaminopropylamine and'y-dibutylaminopropylamine; ethylenediamine, hexamethylenediamine,tetrame thylcnediamine, cyclohexylamine, benzylamine, phenylethylamine;aniline, p-chloroaniline, 3,4-dichloroaniline. 2,4,5- trichloroaniline,p-toluidine, p-dimethylaminoaniline, p-ethylaniline, m-anisidine,p-anisidine, pethoxyaniline; p-aminobenzoic acid, paminobenzamide,p-aminobenz-N,N-dimethylamide, p-aminobenzenesulfonamide;p-benzoylaminoaniline. p-carbomethoxyaniline, p-carboethoxyaniline,pcarbobutoxyaniline, p-phenylenediamine, 4,4- diaminodiphenylmethane,Z-aminobenzothiazole, 2- aminobenzimidazole. 2-aminol-methylbenzimidazole. Z-aminopyridine,2-amino-4-methyl-5-acetylthiazole, 2-amino-4,S-dimethylthiazole,2-amino-4-methyl-5- carbomethoxythiazole,2-amino-4-phenyl-S-carbomethoxythiazole, 2-amino-4,5-di-(p-mcthoxyphenylthiazole. 5-amino-3-methylmercapto-l ,2,4-thiadiazole and5-amino-3-B-carbomethoxyethylmercaptol ,2,4- thiadiazole.

Dyes of the formula (la):

R Ia

\N\ 0 N x in which B is unsubstituted or substituted benzimidazolyl,bcnzothiazolyl. 3,4-dihydro-4-oxoquinazolyl, phenyl, thenyl or furyl;

R is methyl or ethyl;

n is l or 2; and

X is an aliphatic radical of up to twelve carbon atoms, a cycloaliphaticradical or unsubstituted or substituted phenyl; are of specialindustrial significance.

Chloro, methyl, cyano. nitro, carbalkoxy and carbamoyl are preferredsubstituents for the radical B.

Hydroxy. alkoxy, alkanoyloxy, benzoyloxy, dialkylamino and alkylammoniumare preferred substitutents for the aliphatic radical X and alkyl,alkoxy, halogen, carbamoyl. sulfamoyl, carbalkoxy, carboxyl, amino anddialkyl-amino are preferred substituents for the phenyl radical.

Examples of preferred radicals B are: p-nitrophenyl, p-cyanophenyl,benzimidazolyl, 5- methylbenzimidazolyl(2 benzothiazolyl.S-chlorobenzothiazolyl-( 2 3,4-dihydro-4-oxoquinazolyl, 7-chlor0-3.4-dihydro-4-oxoquinazolyl-( 2 5-earbomethoxyphenyl-( 2)5-carboethoxyphcnyl-( 2), 5-carbamoylphenyl (2), 5-carbomethoxyfuryl-(2). 5-carb0ethoxyfuryl-( 2), 5-carboethoxyfuryl-( 2) and5-carbamoylfuryl-( 2).

Specific radicals X include alkyl of three to eight carbon atoms,phenylalkyl of seven to nine carbon atoms, hydroxyalkyl of two to sixcarbon atoms, alkoxyalkyl of a total of three to seven carbon atoms,dialkylaminoalkyl of a total of four to I l carbon atoms,alkylammoniumalkyl ofa total of six to 12 carbon atoms, cyclohexyl,methylcyclohexyl, phenyl and phenyl bearing methyl, ethyl, methoxy,ethoxy, chloro, cyano, earbamoyl, sulfamoyl, carboxyl or dialkylamino ofone to four carbon atoms in the alkyl groups as substituents.

Preferred radicals X are propyl, butyl, hexyl, ,8-ethylhexyl,cyclohexyl, Z-methylcyclohexyl, phenylethyl, B-hydroxyethyl,'y-hydroxypropyl, w-hydroxyphenyl, B-methoxyethyl, p-methoxypropyl,'y-butoxypropyl, pdimethylaminopropyl, y-dibutylaminopropyl,p-trimethylammoniumpropyl, dimethylethylammoniumpropyl,dimethylbenzylammoniumpropyl, phenyl, p-methylphenyl, p-ethylphenyl,p-chlorophenyl, 3,4- dichlorophenyl, p-methoxyphenyl, m-methoxyphenyl,p-ethoxyphenyl, p-sulfamoylphenyl, p-carboxyphenyl, p-cyanophenyl andp-dimethylaminophenyl.

Preferred diamines: X(NH are: pphcnylenediamine,4,4'-diaminodiphenylmethane, ethylenediamine and hexamethylenediamine.

The following Examples illustrate the invention. Referenees to parts andpercentages are by weight unless otherwise stated.

EXAMPLE 1 l6.6 parts of 3-( benzimidazol-2 '-yl )7-diethylaminocoumarinimide and 25.5 parts of pchloroaniline are boiledunder reflux in 60 parts of ethyl glycol for 4 hours. After cooling thedeposited precipitate is suction filtered and washed with ether. l8.7parts (857: of theory) of the compound of the formula:

is obtained which after recrystallization from methyl glycol melts at209 to 2i 1C.

The compounds set out in the following Table l and of the generalformula:

may be prepared analogously:

TABLE 1 Example R R2 Melting point 2 c. .H. cm. to 172C 3 (,H, 200 to202C CH1 4 N c 11 214 to 216C 5 Q OCH, C,H 19s to 197% e Q 0c,H., (2H5197 m lwc 7 Q H 2011 to 203C a Cl (EH 1914 to 200C NH (2H,, 21: to 214%1 1 (2H 2117 11 21uc 12 cH .-c1-1.- (2H3 17s to l77( I Q (2H5 202 to204C OCH,

14 NH, (2H3 2324 m 240C 15 OCH" C1 210 to 212C lb CH 266 m 268C 17 cHcH, (l-1,, 212 234C TABLE l-Continued Example R R2 Melting point is Cso. r-a-| CH1, 3mc

' set out in Table 2 may be prepared by similar methods.

19 -iCH,);-CH;, (H 155 to I57C TABLE 2 20 (CH, N CH 155 m [57C m 2|(CH2, OCHH CH 152 m 54%. Example R' R2 Melting point 22 CH3 CH1. 232 to234 0 27 50m: CJHH 278 to 280C 24 ('oo|-i on. 358 m 360C 19 Q Q-H.s 1K2to 183C EXAMPLE 16.6 parts of 3-( benzimidazol-2'-yl)-7- EXAMPLE 25diethylaminocoumarinimide and 6.9 parts of hydroxy- 16.6 parts of 3-(benzimidazol-2'-yl)-7- lamine hydrochloride are heated to 100C in 55parts diethylaminoeoumarinimide and 2.7 parts of pofmethyl glycol. l2.9parts of ethyldiisopropylamine is phenylenediamine in parts of ethylglycol are boiled then added at this temperature within fifteen minutes.for 5 hours under reflux, and cooled. The precipitate is The whole iskept at 100C for another 3 hours, alsuction filtered and washed withether. l6.2 parts (88% lowed to cool and the precipitate is suctionfiltered. of theory) of the compound of the formula: I62 parts of crudeproduct is obtained which is puriis obtained. It melts at 238 to 240Cafter it has been tied by recrystallization from dimethylformamide. The

recrystallized from methyl glycol. compound has the formula:

EXAMPLE 26 H 15.9 parts of 3-p-cyanophenyl-7- 5 NDdiethylarninocoumarinimidc and 20.6 parts of p- H phenetidinc in 45parts of ethyl glycol are boiled under N O reflux for 6 hours. andcooled. The precipitate is sue- H c tion filtered and washed withalcohol and ether. 17.5 5 2 art: so; rm fth d f 55 p s r o eory) o ecompoun o the formula and melts at 275 to 277C EXAMPLE 3l l6.6 parts ofthe coumarinimide of the formula:

HNI)

is obtained. The substance melts at 147 to 149C after N O NH it has beenrecrystallized from methyl glycol. The com- H C pounds of the generalformula: 3

and 20.6 parts of p-phenetidine in 40 parts of methyl glycol are boiledunder reflux for one hour and cooled. The precipitate is suctionfiltered and washed with water. The product obtained is recrystallizedfrom dimethylformamide. 18.4 parts (8] .57( of theory) of the compoundof the formula:

-Qoc H a c 2 is obtained. The substance melts at 260 to 262C.

The compounds set ou in Table 3 and of the formula:

are obtained by similar methods.

EXAMPLE 42 H5C o H5C in 200 parts of pyridine while stirring. The wholeis stirred for another three hours at room temperature and for 5 hoursat 40C. Then 400 parts of water is added and the deposited precipitateis suction filtered and washed with water. The compound of the formula:

is obtained in a quantitative yield. The substance does not melt below300C after it has been recrystallized from a mixture (l:l) of methylglycol and dimethylformamidc.

dichlorobenzene. 3.6 parts of phenyl isocyanate is allowed to drip in atthis temperature while stirring and the whole is then stirred foranother l 1 hours at 50C. After cooling the product is suction filteredand washed with ether. A quantitative yield of the compound of theformula:

0 N0 NH-CO-NHQ H C 3.9 parts of benzoyl chloride is allowed to drip atroom temperature into a suspension of l l .3 parts of the coumarinderivative of the formula:

is obtained. After recrystallization from dimethylformamide thesubstance melts at 238 to 240C.

Using a similar method the compounds are obtained which are set out inTable 4 and which have the formula:

9 CH SO CH 6 3 M H 2 & 5 (R N O NAR 2 NQ NH-CONHR set out in Table 5 maybe prepared by similar methods.

TABLE 5 Example 12' R2 TABLE 4 Example R R" Melting point 48 C- -H z sl. 44 6 (l (3H5 264 (0 266C 2" 5" Q Ca:- 45 Cu uc l Sl cu, C 11,,

30 46 -(1 (H 3nuc 53 G --C| C2":- EXAMPLE 47 8.8 parts of the coumarinderivative of the formula:

54 cala H 55 l :J:t a CH4 N o o H EXAMPLE 56 8.2 parts of the coumarinderivative of the formula:

is boiled under reflux for 2 hours in 125 parts of ethyl- 50 enechloride with 6.4 parts of dimethyl sulfate and 2.0 parts of magnesiumoxide. Insoluble matter is filtered off and washed with ethylenechloride and the filtrate is concentrated in vacuo so that as a residuethere is ob- N OCH tained l 1.2 parts of the quaternary salt of theformula: H C 5 3 CH ca sof is boiled under reflux in parts of ethylenechloride 0 with an addition of 15.6 parts of diethyl sulfate and 4 Nparts of magnesium'oxide for 22 hours. Insoluble mat- H C ter isfiltered off while hot and washed with ethylene N 0 j chloride. and thefiltrate is concentrated in vacuo. The C1 residue is stirred into 1,500parts of hot water and the 5 2 ,5 solution filtered. A solution of l5parts of zinc chloride in a small amount of water is added and thesolution is saturated with sodium chloride The precipitated zincOuatcrnized compounds of the general formula:

chloride double salt of the formula:

is suction filtered and dried.

EXAMPLE 57 49 parts of the coumarin derivative of the formula CH(CH2)3-N/ 5 \CH H502 is heated at 40 to 50C in 90 parts of dry 0-dichlorobenzene. 3.8 parts of dimethyl sulfate is then allowed to dip inwhile stirring and stirring is continued for another hour at 40 to 50C.After cooling the pre cipitate is suction filtered and washed withether. 6.1 parts (97% of theory) of the quaternary salt of the formula:

9 CH SO EXAMPLE 58 2-( N -p-methoxyphenyl )-imino 3 p-cyanophenyl )-7-diethylaminocoumarin NG- 00H 5 2 A mixture of 2 parts of2-imino-3-pcyanopheny1-7' diethylaminocoumarin and 10 parts ofp-anisidine is stirred for 1 hour at 95C. After cooling to C 200 partsof water is added. After the product has been stirred for another 2hours the product is suction filtered, washed with 200 parts of waterand dried. The yield is 2.6 parts and the melting point is 156C.

' EXAMPLE 59 2-( N-p-methoxyphenyl )-imino3-( 2 '-thenyl-5 carbomethoxy)-7-diethylaminoeoumarin S c0 0 HC 1 w CIT.

N o N/ OCH H c 3 A mixture of 2 parts of 2-imino-3-(2-thenyl-5-carbomethoxy)7-diethy1aminocoumarin and 10 parts of p-anisidine isstirred for 1 hour at C, cooled to about 50C. parts of water is added,the whole is cooled to 5C and the precipitate filtered. The residue isagain stirred in 600 parts of water for three hours, suction filteredand dried. The yield is 2.4 parts and the melting point is to 172C.

EXAMPLE 60 2-( N-p-methoxyphenyl )-imino-3-( 2 '-furyl-5 carbomethoxy)-7-diethylaminocoumarin CO CH H5C 2 j A mixture of 3.4 parts of2-imino-3-(2'-furyl-5- carbomethoxy)-7-diethylaminocoumarin and 10 partsof panisidine is stirred for 2 hours at 95C. After cooling to about 50C150 parts of water is added. The whole is then cooled to 5C and theprecipitate filtered. The residue is again stirred for three hours in600 parts of water. suction filtered and dried. The yield is 2.6 partsand the melting point is 130 to 132C.

EXAMPLE 61 2-( Np-methoxyphenyl )-imino-3-( 2 '-benzothiazo1yl7-diethylaminocoumarin A mixture of 5.2 parts of 2-imino-3-(2'-benzothiazolyl)-7-diethylaminocoumarin and 15 parts of p-anisidine isstirred for 2 hours at 100C. After the whole has cooled to about 25C 300parts of water is added, stirring is continued for another ten hours,and the product is suction filtered. washed with 100 parts of water anddried. It is recrystallized from acetic anhydride. 2.7 parts is obtainedwith a melting point of l84 leum ether 40/60/acetone l: l and drying itthe yield to 185C. is 3.3 parts and the melting point is 250 to 252C.

EXAMPLE 62 EXAMPLE 65 2-( N-p-chlorophenyl )-imino-3-( 2'-thcnyl-5 5 2-[N-(4'-methyl-5 "acetylthiazolyl-2' l-imino-3-pcarbomethoxy)-7-diethylaminocoumarin cyanophenyl-7-diethylaminocoumarin 2 S coca 0 IH C N 5 2 CH A mixture of 3.6 parts of 2-imino-3-(2'-thcnyl-5'-carbomethoxy)-7-diethylaminocoumarin and 10 parts of p-chloroaniline isstirred at 120C for 2 hours. After A solution of 6.3 parts of2-imino-3-p-cyanophenylcooling to about 25C 250 parts of water is added,the 7-diethylaminocoumarin and 3.1 parts of 2-amino-4- whole is stirredfor another 2 hours and suction filtered methyl-S-acetylthiazole in 50parts of diethylene glycol and the product again stirred with 250 partsof water diethyl ether is stirred at 140C for 1 hour, cooled to for 5hours, suction filtered and dried. 4.8 parts of yel- 5C, suctionfiltered and washed with 5 parts of methalow crystals are obtained. Themelting point is 172 to nol. The product is recrystallized from glycolmono- 174C. ethyl ether. 3 parts of yellow crystals are obtained hav- IO O I EXAMPLE 63 mg a me ting pomt of 218 to 220 C 2-(N-benzothiazolyl-2')-imino-3-p-cyanophenyl-7- EXAMPLE 66diethylaminocoumarin The dye of the formula:

ON U H c 5 2\ m coca N (H5C2)2-N 0 N 3 j l N e 5 2 I 0H A solution of4.5 parts of Z-aminobenzothiazole and EXAMPLE 64 The dye of the formula:

is obtained by stirring a solution of 2.3 parts of the dye specified inExample 65 in 50 parts of chlorobenzene and 0.63 part of dimethylsulfate for 10 minutes at 45 C. cooled to 5C, suction filtered anddried. The yield is 2.6 parts and the melting point is 195 to 197C.

EXAMPLE 67 2-[ N-( 3 '-methylmercapto-l ,2,4'-thiadiazolyl-5'imino-3-p-cyanophenyl-7-diethylaminocoumarin I 2 CH 60 5 A mixture of3.2 parts of2-imino-3-p-cyan0phenyl-7 is obtained by stirring a solutionof 4.5 parts of the dye diethylaminocoumarin and 10 parts of 5-amino-3-described in Example 63 in 50 parts of chlorobenzene Mmethylmercapto-l,2,4-thiadiazole is heated to C and .125 parts ofdimethyl sulfate for 10 minutes at and stirred at this temperature for1.25 hours. It is 9()C cooling to 5C and suction filtering theprecipicooled to 50C and 100 parts of methanol is added. It

tated product. After washing it with parts of petrois further cooled to5C. suction filtered and dried. The

yield of orange crystals is 4.4 parts and the melting point is [80 to182C.

EXAMPLE 68 The dye of the formula:

is obtained by stirring a solution of 2.9 parts of the dye described inExample 67 in 50 parts of chlorobenzene and 0.9 part of dimethyl sulfatefor 30 minutes at 90C, cooling to C, suction filtering and drying. Theyield is 3.5 parts and the melting point is l63 to I65C.

We claim: 1. A dye of the formula:

kyl of a total of three to seven carbon atoms. dialkylaminoalkyl of atotal of four to l l carbon atoms, alkylammoniumalkyl of a total of sixto l2 carbon atoms, cyclohexyl, methylcyclohexyl, phenyl and phenylsubstituted by methyl, ethyl, methoxy, ethoxy, chloro, cyano, carbamoyl,sulfamoyl earboxyl, amino or dialkylamino of one to four carbon atoms inthe alkyl groups, or a divalent moiety selected from the groupconsisting of -CH- CH (TH- @EG Q 2. A dye as claimed in claim 1 of theformula:

in which R is methyl or ethyl and X is alkyl of three to eight carbonatoms, cyclohexyl or methylcyclohcxyl. 3. The dye of the formula

1. A DYE OF THE FORMULA:
 2. A dye as claimed in claim 1 of the formula:3. The dye of the formula